CN103387625A - Preparation method and application of polystyrene hollow microspheres - Google Patents
Preparation method and application of polystyrene hollow microspheres Download PDFInfo
- Publication number
- CN103387625A CN103387625A CN201210138993XA CN201210138993A CN103387625A CN 103387625 A CN103387625 A CN 103387625A CN 201210138993X A CN201210138993X A CN 201210138993XA CN 201210138993 A CN201210138993 A CN 201210138993A CN 103387625 A CN103387625 A CN 103387625A
- Authority
- CN
- China
- Prior art keywords
- weight
- polystyrene
- preparation
- phase
- hollow microsphere
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention relates to a preparation method and an application of polystyrene hollow microspheres. According to the invention, polystyrene is dissolved into styrene monomer, such that an oil phase is prepared. The viscosity of the oil phase is controlled by controlling the concentration of polystyrene. In a W1/O/W2 triple emulsion, initiation and polymerization of the styrene monomer, precipitation hardening of polystyrene, and the like are realized, such that the polystyrene hollow microspheres with the hollow structure are formed. The invention also relates to an application of the polystyrene hollow microspheres in drilling fluids and cementing fluids.
Description
Technical field
The present invention relates to a kind of polystyrene hollow microsphere and its preparation method and application.More particularly, the present invention relates to adopt package method to prepare polystyrene hollow microsphere and the application in well drilling industry thereof.
Background technology
The hollow microsphere shaped material, because its special hollow structure has unique chemistry and physical properties, causes people's concern in recent years just more and more, becomes the study hotspot of Material Field.Up to now, inorganic materials, polymer materials, metal oxide materials and semiconductor material (gallium oxide, gan) etc. all are prepared into the hollow microsphere shaped material by researcher trial both at home and abroad, and these materials present the specific function different from corresponding solid material.These hollow microsphere shaped materials with special characteristics are expected to be applied to the aspects such as microreactor, drug conveying, control release, photochemical catalysis, enzyme coating, photonic crystal.In addition, because hollow microsphere shaped material density is low, useful area is large, it is heat insulation to have, sound-absorbing and light hide performance, therefore can be used as density light-weight additive, resin additive and space-filling agent etc., be widely used in industry and the fields such as papermaking, oil production, building coating and biological medicine.
Inorganic Hollow Microspheres is used inorganic materials usually as shell, by methods such as high-temperature digestion and spray method, template, makes, and studies at present the more hollow microspheres such as carbon, silicon-dioxide, titanium dioxide, aluminum oxide, hydroxyapatite that have.Inorganic Hollow Microspheres except having low density characteristics, also has that hardness is high, intensity is high, an outstanding advantages such as corrosion-resistant, Heat stability is good, has a good application prospect.Wherein the glass hollow beads has had ripe industrialization product,, as U.S. Potters company and Belgian Glaverbel company, Pittsburgh Corning company, Minnesota Mining and Manufacturing Company etc., can produce in a large number hollow glass microbead.The glass hollow beads is thin-walled White hollow spheroid, main component is soda-lime, borosilicate glass, density range can be from 0.10g/cm3 to 0.70g/cm3, ultimate compression strength reaches as high as 124MPa, and, along with the development of glass microballon production technology, the intensity that hollow glass microbead can bear can be higher.
The polymer hollow particles shell structure is take organic polymer as main, and its temperature resistance, anti-pressure ability are main relevant with Shell Materials used, and the shell kind of present bibliographical information mainly contains resol, polystyrene, polymethylmethacrylate etc.This hollow microsphere is due to due to wall material self character, has certain deformability, compare with Inorganic Hollow Microspheres, the characteristics that polymer hollow particles is enbrittled is little, toughness is strong, therefore the polymer hollow particles material has better wear-resisting, anti-shear performance, percentage of damage is low under dynamic condition, and this uses significant under dynamic environment for needs, such as petroleum drilling, Cementing etc.Since 21 century, domestic and international researcher has carried out a large amount of research and report to polymer hollow particles, but generally speaking because polymer hollow particles exists still that preparation process is loaded down with trivial details, the spheroid particle diameter controls that difficulty is large, hollow ball shell thickness and phase composite are difficult to the problems such as effectively accurately control, most only limits to the laboratory study stage, also there is no ripe industrialization product.
Of the present inventionly to the effect that utilize improved package method to prepare polystyrene organic hollow microballoon.Package method claims again emulsification-solidification method, is to prepare the most frequently used method of polystyrene hollow microsphere in present domestic literature.Its principle is to adopt three-phase solution: the first water (W1): pure water or pure water+tensio-active agent; Oil phase (O): the homogeneous solution that polystyrene+organic solvent or styrene monomer and coupling agent and initiator mix; The second water (W2): pure water+dispersion agent.Take suitable mode to prepare the W1/O/W2 triple emulsion.Under certain conditions, along with organic solvent in oil phase is diffused into W2 phase or evaporation gradually, or monomer polymerization, oil phase concentration increases gradually until solidify finally formation polystyrene spherical shell fully.So just forming shell is polystyrene, the microballoon of internal package water, and vacuum filtration, washing, packaged water is removed in vacuum-drying, can obtain the polystyrene hollow microsphere.Zhang Lin etc. with polystyrene for becoming ball material, adopting package method to prepare diameter is that 100～300 μ m, wall thickness are the polystyrene hollow microsphere (Zhang Lin of 2～8 μ m, sphericity 〉=95%, concentricity 〉=90%, surfaceness≤300nm, Cui Baoshun, Zhou Lan etc. the standby hollow plastic microsphere of micropackaging legal system. light laser and particle beam, 1995,7(1): 151-156).Tsuji R and Ogushi Y adopt package method to prepare the polystyrene hollow microsphere that can be used as the ICF target, diameter is approximately 520 μ m(Tsuji R, Ogushi Y.Fabrication of polystyrene hollow pellet with high Z microparticles on inner surface for measurement of temperature and density in ICF plasma.Fusion Engineering and Design, 1997,34-35:811-814).
From the above mentioned, at present package method used is mainly realized by three-phased emulsions, and O can be the oil phase of monomer and coupling agent and initiator composition mutually, can be also that polystyrene is dissolved in organic solvent and is made into the O phase.The oil phase of monomer composition does not need with an organic solvent in reaction process, but because the viscosity of monomer is hanged down, is forming the easy breakdown of emulsion of W1/O phase time, and the hollow microsphere particle diameter that forms is less than normal; Be dissolved in organic solvent and be made into O and mainly exist mutually two problem: ⑴ owing in use needing to use organic solvent by polystyrene, environmental and human health impacts is had injury; Therefore ⑵ the viscosity of oil phase is directly proportional to the concentration of polystyrene, and the concentration of polystyrene can not too high (generally being no more than 15%) when the preparation oil phase, otherwise will can not effectively disperse because the O phase viscosity is too large, so output per single reactor is low.
Summary of the invention
The object of the invention is to for addressing the above problem, provide that simple, the hollow breakage rate of a kind of preparation process is low, particle diameter is easily controlled, easy industrialized polystyrene hollow microsphere, and the preparation method and application of this polystyrene hollow microsphere are provided.
Technical scheme of the present invention is:
A kind of preparation method of polystyrene hollow microsphere, it comprises following steps
1) preparation oil phase O: polystyrene is dissolved in styrene monomer, then adds initiator, linking agent and emulsifying agent, stir rear as oil phase; Wherein the weight of polystyrene is 2%～30% of vinylbenzene weight, is preferably 4～20% of vinylbenzene weight; Initiator weight is 0.02～3% of styrene monomer weight, is preferably 0.1～0.5% of styrene monomer weight; Linking agent weight is the 0-3% of styrene monomer weight, is preferably the 0.5-2.5% of styrene monomer weight; The emulsifying agent dosage is the 2-10% of polystyrene and vinylbenzene weight sum, is preferably the 3-5% of polystyrene and vinylbenzene weight sum;
2) preparation W1 phase: after adding emulsifiers dissolve evenly in distilled water, as the W1 phase, the weight of emulsifying agent is the 0.5-8% of distilled water weight, is preferably the 2-5% of distilled water weight;
3) preparation W2 phase: add dispersion agent and emulsifying agent in distilled water, be uniformly dissolved rear as the W2 phase; The weight of the dispersion agent that adds is the 0.12-8% of distilled water weight, is preferably the 1-3% of distilled water weight; The weight of the emulsifying agent that adds is the 0-1.0% of distilled water weight, is preferably the 0.1-0.3% of distilled water weight;
4) W1 is added to O mutually in, fully emulsified, make the W1/O emulsion, the W1 phase is 1:5.2-1:1.7 with the mass ratio of O phase, is preferably 1:2.5-1:3;
5) under water bath condition, control temperature at room temperature condition, with the W1/O emulsion evenly spread to W2 mutually in, the W1/O emulsion is not more than 1: 2.5 with the mass ratio of W2 phase, preferred 1: 5～1: 7; Namely start after being uniformly dispersed to heat up, bath temperature is risen to 70-95 ℃, preferred 75-80 ℃, reacted 4 hours at least, preferred 6-9 hour; Rear end reaction, keep liquid phase to be in dynamic scatter in whole reaction process, utilize the suction filtration device with the product suction filtration; To take out product oven dry caught on a filter and namely obtain product.
The state of above-mentioned dynamic scatter keeps the emulsion can not be static exactly, can adopt stirring, ultrasonic or with little pump, do not stop circulation etc., until monomer polymerization solidifies.If, because liquid phase is not static before reaction is completed, will cause creaming of emulsion or destruction.
Above-mentioned steps 1) polystyrene that uses in is polystyrene waste or used plastics and/or industrialization product polystyrene raw material;
Above-mentioned steps 1) initiator that uses in is selected from least a in azo-initiator, organic peroxy class initiator, inorganic peroxy class initiator or oxidation-reduction initiator.
Above-mentioned steps 1) linking agent that uses in is selected from divinylbenzene, vulcabond, a kind of in N,N methylene bis acrylamide (MBA) or ethylene glycol dimethacrylate.
Above-mentioned steps 1) emulsifying agent that uses in is selected from the emulsifying agent of HLB scope between 3-8, at least a in class of preferred department 80, class 60 of department or glycerin fatty acid ester.
Above-mentioned steps 2) emulsifying agent that uses in comprises at least a in sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate or OP-10.
Above-mentioned steps 3) dispersion agent that uses in comprises at least a in xanthan gum, gelatin, carboxymethyl cellulose, Polyvinylpyrolidone (PVP), Natvosol or polyvinyl alcohol.
Above-mentioned steps 3) emulsifying agent that uses in comprises at least a in sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, class of department 80, class 60 of department or OP-10.
Above-mentioned steps 4) emulsification in can be adopted mode (rotating speed 〉=1000r/min, the preferred 9000r/min of stirring; Stir 2-20min, preferred 5-10min) or utilize the SPG film to carry out emulsification or carry out ultrasonic emulsification.
Above-mentioned steps 5) dispersion can be adopted ultra-sonic dispersion mode, SPG film emulsifying manner or alr mode.
A kind of polystyrene hollow microsphere according to above-mentioned preparation method's preparation, this microballoon had both comprised the polystyrene of the not commissure that adds early stage, also comprised the polystyrene that the later stage is generated by the styrene monomer polymerization.
The application of the polystyrene hollow microsphere of aforesaid method preparation:
The polystyrene hollow microsphere is as the application of fluid light-weight additive in low density drilling fluid, wherein, directly add the polystyrene hollow microsphere and be uniformly dispersed in drilling fluid, the add-on of polystyrene hollow microsphere is preferably every 100ml drilling fluid and adds polystyrene hollow microsphere 1-30g.
The polystyrene hollow microsphere is as the application of fluid light-weight additive in low-density well cementing liquid, wherein, directly add the polystyrene hollow microsphere and be uniformly dispersed in cementing fluid, the add-on of polystyrene hollow microsphere is preferably every 100ml drilling fluid and adds polystyrene hollow microsphere 1-30g.
Beneficial effect of the present invention is:
1) dissolve appropriate polystyrene in vinylbenzene and can improve monomer viscosity, the emulsion instability problem of having avoided simple use monomer to cause because viscosity is too low, can prepare the greater particle size product, and more be conducive to formation and the maintenance of hollow structure.
2) do not need with an organic solvent, do not have the recovery of solvent and utilize problem, Safety and Environmental Protection is good.
3) due to styrene monomer under the effect of initiator too polymerization generate polystyrene, therefore good with original polystyrene consistency, oil phase can all be converted into product, output per single reactor is high, and it is dimerous that the polystyrene hollow microsphere of generation is actually the polystyrene composition that is generated by original polystyrene composition and later stage polymerization.
4) the polystyrene hollow microsphere particle diameter of preparing with package method is even, and the product circularity is good, product cut size can by adjust W1 mutually in emulsifying agent dosage, W1/O ratio, dispersant, dispersant dosage, stirring velocity control;
5) the method can utilize discarded polystyrene as one of raw material, on the one hand reaction is easily carried out, and has reduced again the monomer usage quantity, saves cost, also can be used as the novel method of a kind of recycling of " white pollution ";
6) the recyclable recycling of water used in preparation process, reduced cost, also for the Realization of Product industrialization, provides possibility.
Description of drawings
Fig. 1 is the polystyrene plastic bead stereoscan photograph of embodiment 5 preparations
Fig. 2 is the stereoscan photograph of internal structure of the polystyrene plastic bead of embodiment 5 preparation.
Embodiment
Embodiment 1
With computer packaging polystyrene foamed plastics wash clean, dry for standby;
1) configuration oil phase: take the above-mentioned clean polystyrene foamed plastics of 7.38g, add styrene monomer 24.6g and benzoyl peroxide 0.738g, add ethylene glycol dimethacrylate 0.615, the 603.198g of class of department, make oil phase after mixing; Wherein 30% of polystyrene weight styrene monomer weight, initiator is 3.0% of styrene monomer weight; Linking agent weight is 2.5% of styrene monomer weight, and emulsifying agent weight is 10% of polystyrene weight and styrene monomer weight sum, and O phase total mass is 36.531g;
2) configuration W1 phase: get 7.0g distilled water, add the 0.035g Sodium dodecylbenzene sulfonate, be uniformly dissolved afterwards as the W1 phase, emulsifying agent weight is 0.5% of distilled water weight, and W1 phase total mass is 7.035g;
3) configuration W2 phase: the 16g polyvinyl alcohol is joined in 200ml distilled water, stir; Dispersion agent weight is 8% of distilled water weight, and emulsifying agent weight is 0% of distilled water weight, and W2 phase total mass is 108g;
4) W1 is added to O under whipped state and is mixed with even W1/O emulsion in mutually, emulsion, stirring velocity are 6000r/min, stir 5min, and W1 phase quality is 1:5.2 with O phase mass ratio;
5) W2 is poured into mutually in reactor with condensing works (prolong) (as there-necked flask), put into water-bath, under agitation condition with the W1/O emulsion dispersion of ⑷ section preparation to W2 mutually in, after stablizing 15min, temperature is risen to 85 ℃, be warming up to 95 ℃ after keeping stirring 4h, keep after 2 hours and finish, W1+O phase quality is 1:5.0 with W2 phase mass ratio;
6) will take out product oven dry caught on a filter and namely obtain product, the products obtained therefrom particle size average is 179 μ m.
Embodiment 2
With computer packaging polystyrene foamed plastics wash clean, dry for standby;
1) configuration oil phase: take the above-mentioned clean polystyrene foamed plastics of 0.63g, add styrene monomer 31.5g, benzoyl peroxide 0.0063g, the 800.65g of class of department, mix and make oil phase.Polystyrene is 2% of vinylbenzene weight, and initiator is 0.02% of styrene monomer weight, and coupling agent weight is 0% of styrene monomer weight, and class of department 80 weight are 2% of polystyrene and styrene monomer weight sum, and the oil phase total mass is 32.78g;
2) configuration W1 phase: get 18.0g distilled water, add the 1.44g sodium laurylsulfonate, be uniformly dissolved afterwards as the W1 phase, emulsifying agent weight is 8% of distilled water weight, and W1 phase total mass is 19.44g;
3) configuration W2 phase: 0.156g gelatin, 0.11g Sodium dodecylbenzene sulfonate and 0.02g sorbitol anhydride oleate are joined in 130ml distilled water, stir and make water; Dispersion agent weight is 0.12% of water weight, and emulsifying agent weight is 0.1% of water weight, and W2 phase total mass is 130.286g;
4) W1 is added to O under whipped state and is mixed with even W1/O emulsion in mutually, stirring velocity is 9000r/min, stirs 2min, and W1 phase quality is 1:1.7 with O phase mass ratio;
5) W2 is poured into mutually in reactor with condensing works (prolong) (as there-necked flask), put into water-bath, the adjustment rotating speed is 300r/min, under agitation condition with the W1/O emulsion dispersion of ⑷ section preparation to W2 mutually in, after stablizing 15min, temperature is risen to 85 ℃, keep after stirring 6h and be warming up to 90 ℃, keep and finish to finish after 3 hours; W1+O phase quality is 1:2.5 with W2 phase mass ratio;
6) with the vacuum filtration device, described emulsion is carried out suction filtration and separate, isolate bead, namely obtain the polystyrene hollow microsphere that median size is 93 μ m after 70 ℃ of oven dry 24h.
Embodiment 3
With computer packaging polystyrene foamed plastics wash clean, dry for standby;
1) configuration oil phase: take the above-mentioned clean polystyrene foamed plastics of 4g, add styrene monomer 100 and benzoyl peroxide 0.5g, add ethylene glycol dimethacrylate 3g, the 605.2g of class of department, make oil phase after mixing; Wherein 4% of polystyrene weight styrene monomer weight, initiator is 0.5% of styrene monomer weight; Coupling agent weight is 3% of styrene monomer weight, and emulsifying agent weight is 5% of polystyrene weight and styrene monomer weight sum, and O phase quality sum is 112.7g;
2) configuration W1 phase: get 43g distilled water, add the 1.15g sodium lauryl sulphate, 1.0gOP-10, be uniformly dissolved afterwards as the W1 phase, and emulsifying agent weight is 5% of distilled water weight, and W1 phase total mass is 45.15g;
3) configuration W2 phase: the 32.1g polyvinyl alcohol is joined in 1070ml distilled water, then add the 10.7g sodium lauryl sulphate, stir as water; Dispersion agent weight is 3% of water weight, and emulsifying agent weight is 1.0% of water weight, and W2 phase quality is 1112.8g;
4) W1 is added to O under whipped state and is mixed with even W1/O emulsion in mutually, stirring velocity is 1000r/min, stirs 20min, and W1 phase quality is 1:2.5 with O phase mass ratio;
5) W2 is poured into mutually in reactor (as there-necked flask) with condensing works (as prolong), put into water-bath, the adjustment rotating speed is 300r/min, under agitation condition with the W1/O emulsion dispersion of ⑷ section preparation to W2 mutually in, after stablizing 15min, temperature is risen to 75 ℃, keep to stir after 7 hours that temperature is risen to 90 ℃, keep after 3 hours and finish; W1+O phase quality is 1:7.0 with W2 phase mass ratio;
6) with the vacuum filtration device, described emulsion is carried out suction filtration and separate, isolate bead, namely obtain the polystyrene hollow microsphere that median size is 107 μ m after 70 ℃ of oven dry 24h.
Embodiment 4
With computer packaging polystyrene foamed plastics wash clean, dry for standby;
1) configuration oil phase: take the above-mentioned clean polystyrene foamed plastics of 8g, add styrene monomer 40g, Diisopropyl azodicarboxylate 0.04g, the 801.44g of class of department, EGDMA 1.2g mixes and makes oil phase; Polystyrene is 20% of vinylbenzene weight, and initiator is 0.1% of styrene monomer weight, and coupling agent weight is 3% of styrene monomer weight, and emulsifying agent weight is 2% of polystyrene and styrene monomer weight sum, and O phase quality is 50.68g;
2) configuration W1 phase: get 17g distilled water, add 0.34g OP-10, be uniformly dissolved afterwards as the W1 phase, emulsifying agent weight is 2% of distilled water weight, and W1 phase total mass is 17.34g;
3) configuration W2 phase: with the 3g gelatin, 1.05g polyvinyl alcohol, 0.7g sodium lauryl sulphate and 0.515g sorbitol anhydride oleate join in 405ml distilled water, stir and make water; Dispersion agent weight is 1.0% of water weight, and emulsifying agent weight is 0.3% of water weight, and W2 phase quality is 410.265;
4) W1 is added to O under whipped state and is mixed with even W1/O emulsion in mutually, stirring velocity is 5000r/min, stirs 10min, and W1 phase quality is 1:3.0 with O phase mass ratio;
5) W2 is poured into mutually in reactor with condensing works (prolong) (as there-necked flask), put into water-bath, the adjustment rotating speed is 300r/min, under agitation condition with the W1/O emulsion dispersion of ⑷ section preparation to W2 mutually in, after stablizing 15min, temperature is risen to 70 ℃, after keeping stirring 4h, temperature is risen to 90 ℃, keep after 3 hours and finish; W1+O phase quality is 1:6.0 with W2 phase mass ratio;
6) with the vacuum filtration device, described emulsion is carried out suction filtration and separate, isolate bead, namely obtain the polystyrene hollow microsphere that median size is 92 μ m after 70 ℃ of oven dry 24h.
Embodiment 5
Get China Petrochemical Industry's Yanshan Petrochemical product: polystyrene, the trade mark: 666D is standby;
1) configuration oil phase: take the above-mentioned clean polystyrene foamed plastics of 8g, add styrene monomer 40g, Diisopropyl azodicarboxylate 0.02g, class of department 600.60g, glycerin fatty acid ester 0.60g, EGDMA 0.2g mixes and makes oil phase; Polystyrene is 20% of vinylbenzene weight, and initiator is 0.05% of styrene monomer weight, and coupling agent weight is 0.5% of styrene monomer weight, and oil-soluble emulsifier weight is 3% of polystyrene and styrene monomer weight sum, and O phase quality is 49.42g;
2) configuration W1 phase: get 17g distilled water, add the 0.34g sodium lauryl sulphate, be uniformly dissolved afterwards as the W1 phase, emulsifying agent weight is 2% of distilled water weight, and W1 phase total mass is 17.34g;
3) configuration disperses water: with the 3g gelatin, 1g polyvinyl alcohol, 1.2g Potassium Persulphate, 0.7g sodium lauryl sulphate and 0.5g sorbitol anhydride oleate, join in 400ml distilled water, stirs and make water; Dispersion agent weight is 1.0% of water weight, and emulsifying agent weight is 0.3% of water weight, and water soluble starter is 3% of monomer mass; The quality of W2 phase is 406.4g;
4) W1 is added to O under whipped state and is mixed with homogeneous latex emulsion in mutually, stirring velocity is 5000r/min, stirs 10min, and W1 phase quality is 1:2.9 with O phase mass ratio;
5) above gained emulsion is transferred in the SPG membrane emulsifier of 20 μ m, foreign minister's solution is the W2 phase, by film emulsification, obtains uniform three-phased emulsions; Three-phased emulsions is transferred in flask, stirred and be warming up to 60 ℃ under the rotating speed of 350r/min, keep and stir 5h; Temperature is risen to 85 ℃, keep after stirring 3h and finish; W1+O phase quality is 1:6.1 with W2 phase mass ratio;
6 use vacuum filtration devices carry out suction filtration with described emulsion to be separated, and isolates bead, namely obtains the polystyrene hollow microsphere that median size is 87 μ m after 70 ℃ of oven dry 24h.
The bead that makes characterizes through scanning electronic microscope, (300 times of this picture magnifications) as shown in Figure 1, as seen even with the plastic pellet particle diameter of the method preparation from scheming, the product circularity is good, and product cut size can be controlled also and can control particle diameter by senior emulsification means SPG membrane emulsifier in oil phase mass ratio, W2 phase dispersant dosage, stirring velocity etc. by adjusting W1.Internal structure is (1047 times of this picture magnifications) as shown in Figure 2, and obvious from the hollow microsphere hollow structure of scheming visible the method preparation, wall thickness is even.
Embodiment 6
Get a beaker, add the 0.4g xanthan gum as carrying stick in the 200ml tap water, add the polystyrene hollow plastic bead of 20g embodiment 5 preparations after being uniformly dissolved, namely join to obtain low density drilling fluid after stirring.This drilling fluid density is 0.91g/cm
3.The measuring method of drilling fluid density is seen GB/T 16783-1997 " water-base drilling fluid On-Site Test Procedure " " 1 drilling fluid density.So hollow polystyrene plastic bead of the present invention can be used as the light-weight additive of drilling fluid and uses.
Claims (12)
1. the preparation method of a polystyrene hollow microsphere, it comprises following steps:
1) preparation oil phase O: polystyrene is dissolved in styrene monomer, then adds initiator, linking agent, emulsifying agent, stir rear as oil phase; Wherein the weight of polystyrene is 2%～30% of vinylbenzene weight, is preferably 4～20% of vinylbenzene weight; Initiator weight is 0.02～3% of styrene monomer weight, is preferably 0.1～0.5% of styrene monomer weight; Linking agent weight is the 0-3% of styrene monomer weight, is preferably the 0.5-2.5% of styrene monomer weight; The emulsifying agent dosage is the 2-10% of polystyrene and vinylbenzene weight sum, is preferably the 3-5% of polystyrene and vinylbenzene weight sum;
2) preparation W1 phase: after adding emulsifiers dissolve evenly in distilled water, as the W1 phase, the weight of emulsifying agent is the 0.5-8% of distilled water weight, is preferably the 2-5% of distilled water weight;
3) preparation W2 phase: add dispersion agent and emulsifying agent in distilled water, be uniformly dissolved rear as the W2 phase; The weight of the dispersion agent that adds is the 0.12-8% of distilled water weight, is preferably the 1-3% of distilled water weight; The weight of the emulsifying agent that adds is the 0-1.0% of distilled water weight, is preferably the 0.1-0.3% of distilled water weight;
4) W1 is added to O mutually in, fully emulsified, make the W1/O emulsion, the W1 phase is 1:5.2-1:1.7 with the mass ratio of O phase, is preferably 1:2.5-1:3;
5) under water bath condition, control temperature at room temperature condition, with the W1/O emulsion evenly spread to W2 mutually in, the W1/O emulsion is not more than 1: 2.5 with the mass ratio of W2 phase, preferred 1: 5～1: 7; Namely start after being uniformly dispersed to heat up, bath temperature is risen to 70-95 ℃, preferred 75-80 ℃, reacted 4 hours at least, and preferred the end after 6-9 hour reacts, and keeps liquid phase to be in dynamic scatter in whole reaction process, utilizes the suction filtration device with the product suction filtration; To take out product oven dry caught on a filter and namely obtain product.
2. preparation method according to claim 1, is characterized in that, described step 1) in the polystyrene that uses be polystyrene waste or used plastics and/or industrialization product polystyrene raw material.
3. preparation method according to claim 1 and 2, is characterized in that, described step 1) in the initiator that uses be selected from least a in azo-initiator, organic peroxy class initiator, inorganic peroxy class initiator or oxidation-reduction initiator.
4. preparation method according to claim 1 and 2, is characterized in that, described step 1) in a kind of in the preferred divinylbenzene of linking agent, vulcabond, N,N methylene bis acrylamide or the ethylene glycol dimethacrylate that use.
5. preparation method according to claim 1 and 2, is characterized in that, described step 1) in the oil-soluble emulsifier that uses be selected from the emulsifying agent of HLB scope between 3-8, at least a in class of preferred department 80, class 60 of department or glycerin fatty acid ester.
6. preparation method according to claim 1 and 2, is characterized in that, described step 2) in the emulsifying agent that uses comprise at least a in sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate or OP-10.
7. preparation method according to claim 1 and 2, is characterized in that, described step 3) in the dispersion agent that uses comprise at least a in xanthan gum, gelatin, carboxymethyl cellulose, Polyvinylpyrolidone (PVP), Natvosol or polyvinyl alcohol.
8. preparation method according to claim 1 and 2, is characterized in that, described step 3) in the emulsifying agent that uses comprise at least a in sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, class of department 80, class 60 of department or OP-10.
9. preparation method according to claim 1 and 2, is characterized in that, described step 4) in emulsification adopt the mode of high-speed stirring or utilize the SPG film to carry out emulsification or carry out ultrasonic emulsification.
10. preparation method according to claim 1 and 2, is characterized in that, described step 5) dispersion adopt ultra-sonic dispersion mode, SPG film emulsifying manner or alr mode.
11. the polystyrene hollow microsphere of preparation method's preparation according to claim 1 and 2 is as the application of fluid light-weight additive in low density drilling fluid, wherein, directly add the polystyrene hollow microsphere and be uniformly dispersed in drilling fluid, the add-on of polystyrene hollow microsphere is preferably every 100ml drilling fluid and adds polystyrene hollow microsphere 1-30g.
12. the polystyrene hollow microsphere of preparation method's preparation according to claim 1 and 2 is as the application of fluid light-weight additive in low-density well cementing liquid, wherein, directly add the polystyrene hollow microsphere and be uniformly dispersed in cementing fluid, the add-on of polystyrene hollow microsphere is preferably every 100ml drilling fluid and adds polystyrene hollow microsphere 1-30g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210138993.XA CN103387625B (en) | 2012-05-07 | 2012-05-07 | The preparation method of polystyrene hollow microsphere and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210138993.XA CN103387625B (en) | 2012-05-07 | 2012-05-07 | The preparation method of polystyrene hollow microsphere and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103387625A true CN103387625A (en) | 2013-11-13 |
| CN103387625B CN103387625B (en) | 2015-09-02 |
Family
ID=49532057
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210138993.XA Active CN103387625B (en) | 2012-05-07 | 2012-05-07 | The preparation method of polystyrene hollow microsphere and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103387625B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103387691A (en) * | 2012-05-08 | 2013-11-13 | 中国石油化工股份有限公司 | Hollow polystyrene plastic spheres, and preparation method and application thereof |
| CN103666407A (en) * | 2012-09-12 | 2014-03-26 | 中国石油化工股份有限公司 | Drilling fluid and preparation method thereof |
| CN105504566A (en) * | 2016-01-26 | 2016-04-20 | 西南科技大学 | Preparation method of columnar styrene and divinyl benzene copolymer hydrophobic catalyst carrier |
| CN107522477A (en) * | 2017-08-24 | 2017-12-29 | 浙江科屹耐火材料有限公司 | A kind of complex intensifying core shell structure refractory brick and its preparation technology |
| CN107686339A (en) * | 2017-08-29 | 2018-02-13 | 浙江攀盛冶金材料有限公司 | A kind of high magnesia refractories for tundish |
| CN108129599A (en) * | 2016-12-01 | 2018-06-08 | 广州蓝月亮实业有限公司 | A kind of surface has microchannel hollow polymer plastic microballoon and its preparation method and application |
| CN108129602A (en) * | 2016-12-01 | 2018-06-08 | 广州蓝月亮实业有限公司 | A kind of surface has microchannel hollow polymer elastic microsphere and its preparation method and application |
| CN108164631A (en) * | 2018-01-12 | 2018-06-15 | 东华大学 | Styrene-bifunctionality monomer copolymer hollow porous micro sphere and preparation method |
| CN110872505A (en) * | 2019-12-03 | 2020-03-10 | 成都理工大学 | Organic porous nano-particle/surfactant composite oil displacement system and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1587286A (en) * | 2004-07-08 | 2005-03-02 | 清华大学 | Radiation dispersion polymerization process of phenylethylene micro ball |
| CN1688669A (en) * | 2002-08-14 | 2005-10-26 | 3M创新有限公司 | Drilling fluid containing microspheres and use thereof |
| CN1834120A (en) * | 2005-03-17 | 2006-09-20 | 中国科学院过程工程研究所 | Prepn. of magnetic molecular pellets by complex emulsion process (W1/0/W2 type) |
| CN1903890A (en) * | 2005-07-27 | 2007-01-31 | 中国科学院过程工程研究所 | Preparation method of super large pore polymer microsphere and its product |
| CN101688111A (en) * | 2007-06-18 | 2010-03-31 | 3M创新有限公司 | Reduce the additive of the flow losses of drilling fluid |
| CN102391400A (en) * | 2011-06-21 | 2012-03-28 | 中国航空工业集团公司北京航空材料研究院 | Preparation method of micron-grade monodisperse polystyrene microspheres |
-
2012
- 2012-05-07 CN CN201210138993.XA patent/CN103387625B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1688669A (en) * | 2002-08-14 | 2005-10-26 | 3M创新有限公司 | Drilling fluid containing microspheres and use thereof |
| CN1587286A (en) * | 2004-07-08 | 2005-03-02 | 清华大学 | Radiation dispersion polymerization process of phenylethylene micro ball |
| CN1834120A (en) * | 2005-03-17 | 2006-09-20 | 中国科学院过程工程研究所 | Prepn. of magnetic molecular pellets by complex emulsion process (W1/0/W2 type) |
| CN1903890A (en) * | 2005-07-27 | 2007-01-31 | 中国科学院过程工程研究所 | Preparation method of super large pore polymer microsphere and its product |
| CN101688111A (en) * | 2007-06-18 | 2010-03-31 | 3M创新有限公司 | Reduce the additive of the flow losses of drilling fluid |
| CN102391400A (en) * | 2011-06-21 | 2012-03-28 | 中国航空工业集团公司北京航空材料研究院 | Preparation method of micron-grade monodisperse polystyrene microspheres |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103387691A (en) * | 2012-05-08 | 2013-11-13 | 中国石油化工股份有限公司 | Hollow polystyrene plastic spheres, and preparation method and application thereof |
| CN103666407A (en) * | 2012-09-12 | 2014-03-26 | 中国石油化工股份有限公司 | Drilling fluid and preparation method thereof |
| CN103666407B (en) * | 2012-09-12 | 2016-08-24 | 中国石油化工股份有限公司 | Drilling fluid and preparation method thereof |
| CN105504566A (en) * | 2016-01-26 | 2016-04-20 | 西南科技大学 | Preparation method of columnar styrene and divinyl benzene copolymer hydrophobic catalyst carrier |
| CN105504566B (en) * | 2016-01-26 | 2018-01-16 | 西南科技大学 | A kind of preparation method of column styrene divinylbenzene copolymer hydrophobic catalyst carrier |
| CN108129599B (en) * | 2016-12-01 | 2020-11-20 | 广州蓝月亮实业有限公司 | Hollow polymer plastic microsphere with micro-channels on surface and preparation method and application thereof |
| CN108129599A (en) * | 2016-12-01 | 2018-06-08 | 广州蓝月亮实业有限公司 | A kind of surface has microchannel hollow polymer plastic microballoon and its preparation method and application |
| CN108129602A (en) * | 2016-12-01 | 2018-06-08 | 广州蓝月亮实业有限公司 | A kind of surface has microchannel hollow polymer elastic microsphere and its preparation method and application |
| CN108129602B (en) * | 2016-12-01 | 2020-11-20 | 广州蓝月亮实业有限公司 | Hollow polymer elastic microsphere with micro-channels on surface and preparation method and application thereof |
| CN107522477A (en) * | 2017-08-24 | 2017-12-29 | 浙江科屹耐火材料有限公司 | A kind of complex intensifying core shell structure refractory brick and its preparation technology |
| CN107686339A (en) * | 2017-08-29 | 2018-02-13 | 浙江攀盛冶金材料有限公司 | A kind of high magnesia refractories for tundish |
| CN108164631B (en) * | 2018-01-12 | 2019-07-19 | 东华大学 | Styrene-bifunctionality monomer copolymer hollow porous micro sphere and preparation method |
| CN108164631A (en) * | 2018-01-12 | 2018-06-15 | 东华大学 | Styrene-bifunctionality monomer copolymer hollow porous micro sphere and preparation method |
| CN110872505A (en) * | 2019-12-03 | 2020-03-10 | 成都理工大学 | Organic porous nano-particle/surfactant composite oil displacement system and preparation method thereof |
| CN110872505B (en) * | 2019-12-03 | 2020-09-15 | 成都理工大学 | Organic porous nano-particle/surfactant composite oil displacement system and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103387625B (en) | 2015-09-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103387717B (en) | A kind of organic/inorganic composite hollow microballoon and its preparation method and application | |
| CN103387625B (en) | The preparation method of polystyrene hollow microsphere and application thereof | |
| CN103421253B (en) | The preparation method of polystyrene hollow microsphere and application thereof | |
| CN103387691B (en) | A kind of hollow polystyrene plastic pellet and its preparation method and application | |
| CN105399889B (en) | A kind of hydridization wall material Nano capsule of phase-changing energy storage material and preparation method thereof | |
| CN104624132B (en) | Epoxy resin self-repairing microcapsule and preparation method thereof | |
| CN103665747B (en) | A kind of compound hollow microballoon and its preparation method and application | |
| CN103509143B (en) | The preparation method of organic/inorganic composite pellets | |
| CN100543052C (en) | The preparation method of nano-level crosslinked polystyrene hollow microsphere | |
| CN104844751A (en) | Micron-sized cross-linked polymer hollow microspheres and preparation method for same | |
| CN106751977A (en) | Heat-resisting pitch micro-crack selfreparing microcapsules high and preparation method thereof | |
| CN107099210A (en) | A kind of anticracking waterproof coating and preparation method | |
| CN104403058A (en) | Latex plugging agent for drilling fluid and preparation method thereof | |
| CN106214489A (en) | A kind of double-deck emulsion droplet, medicine carrying microballoons and preparation method thereof and device | |
| CN103342991A (en) | Composite nanocapsule phase-change material and preparation method thereof | |
| Wang et al. | Pickering emulsion of metal-free photoinduced electron transfer-ATRP stabilized by cellulose nanocrystals | |
| CN107417855A (en) | A kind of organic inorganic hybridization emulsion particle toughness reinforcing hydrophobic association hydrogel and preparation method thereof | |
| CN103585936B (en) | A kind of preparation method of plastic hollow bead and its product prepared and application | |
| CN104194003A (en) | Method for preparing black monodisperse polymer microspheres | |
| CN104072656A (en) | Method for preparing ferroferric oxide-macromolecule magnetic composite microspheres | |
| CN103804558A (en) | Nano phase change material emulsion wide in temperature change range and preparation method thereof | |
| CN104193991A (en) | Graphene quantum dot polyaniline composite material and preparation method thereof | |
| CN106589406B (en) | A method of preparing wax dispersions and paraffin microballoon by stabilizer of polymer microballoon | |
| CN102344517B (en) | Polymer microballoons and preparation method thereof | |
| CN101407565A (en) | Soy protein / emulsion polymerization high polymer nano composite material, and preparation and use thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |